1-phenyl-2-cyanovinyl(thio)-phosphoric or-phosphonic acid esters

ABSTRACT

IN WHICH   X IS OXYGEN OR SULFUR, R1 IS LOWER ALKYL, R2 IS LOWER ALKYL OR ALKOXY, PHENYL OR LOWER MONOALKYLAMINO, AND R3 IS HYDROGEN, HALOGEN, LOWER ALKYL, ALKOXY OR ALKYLMERCAPTO,   WHICH POSSESS INSECTICIDAL, ACARICIDAL, ECTOPARASITICIDAL, FUNGICIDAL, BACTERICIDAL AND RODENTICIDAL PROPERTIES. 1-PHENYL-2-CYANOVINYL(THIO)-PHOSPHORIC OR -PHOSPHONIC ACID ESTERS OF THE GENERAL FORMULA   NC-CH=C(-C6H4-R3)-O-P(=X)(-R2)-O-R1

United States Patent 3,763,285 l-PHENYL-Z-CYANOVINYL(THIO)-PHOSPHORIC 0R -PHOSPHONIC ACID ESTERS Hans-Jochem Riebel, Wuppertal-Elberfeld, Ingeborg Hammann, Cologne, Giinter Unterstenhiifer, Opladen, Wolfgang Behrenz, Cologne, and Wilhelm Stendel, Wuppertal-Elberfeltl, Germany, assignors to Bayer Aktiengesellschaft, Leverkusen, Germany No Drawing. Filed June 7, 1971, Ser. No. 150,847 Claims priority, application Germany, June 20, 1970, P 20 30 509.3 Int. Cl. A01n 9/36; C07f 9/16 US. Cl. 260-940 9 Claims ABSTRACT OF THE DISCLOSURE l-phenyl-Z-cyanovinyl(thio)-phosphoric or -phosphonic acid esters of the general formula X is oxygen or sulfur,

R is lower alkyl,

R is lower alkyl or alkoxy, phenyl or lower monoalkylamino, and

R is hydrogen, halogen, lower alkyl, alkoxy or alkylmercapto,

which possess insecticidal, acaricidal, ectoparasiticidal, fungicidal, bactericidal and rodenticidal properties.

The present invention relates to and has for its objects the provision of particular new l-phenyl-Z-cyanovinyl- (thio)-phosphoric or -phosphonic acid esters i.e. lower alkyl esters of l-(optionally halogen-, lower alkyl-, alkoxyor alkylmercapto-)phenyl-Z-cyanovinyl(thio)-phosphoric or alkanephosphonic acids or monoalkylamides, which possess insecticidal, acaricidal, ectoparasiticidal, fungicidal, bactericidal and rodenticidal properties, active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such compounds in a new way especially for combating pests, e.g. insects, acarids, ectoparasites, fungi, bacteria and rodents, especially insects and acarids, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

It is known that 2-chloro-1-(2,4,5-trichlorophenyl)- vinyldimethyl-phosphate (Compound A, cf. US. patent specification 3,102,842), 2-chloro-1-(2,4-dichlorophenyl)- vinyldiethyl-phosphate (Compound B, cf. US. patent specification 3,003,916) and 2-cyano-2-phenyl-l-methyldiethylthiophosphate (Compound C, cf. Y. Nishizawa, Bull. Agr. Chem. Soc. Japan, 25, 61 [1961] and published Japanese patent application 2,926 [1960]) exhibit insecticidal properties.

The present invention provides the new l-phenyl-Z- cyanovinyl(thio)-phosphoric or -phosphonic acid derivatives of the general formula I ll No-on=o-0-P 3,763,285 Patented Oct. 2, 1973 in which X is oxygen or sulfur,

R is lower alkyl,

R is lower alkyl or alkoxy, phenyl or lower monoalkylamino, and

R is hydrogen, halogen, lower alkyl, alkoxy or alkylmercapto.

These compounds exhibit strong insecticidal and acaricidal properties.

It will be understood that the general Formula I includes the corresponding cis and trans isomers of the constitutions (II) and (III) H NC C=C C=N OR OR 1 as well as mixtures thereof.

R is preferably alkyl with 1 to 4 and especially 1 to 3 carbon atoms. R is preferably alkyl or alkoxy with 1 to 4 and especially 1 to 3 carbon atoms, or phenyl, or monoalkylamino with 1 to 4 and especially 1 t0 3 carbon atoms. R is preferably hydrogen, chlorine, bromine, alkyl, alkoxy, or alkylmercapto groups with, in each case, 1 to 4 carbon atoms.

The present invention also provides a process for the production of a 2-cyanovinyl- (thio)-phosphoric or -phosphonic acid derivative of the Formula I in which R has the meaning stated above,

in which is reacted, optionally in the form of an alkali metal salt or in the presence of an acid-binding agent and optionally in the presence of a solvent, with a phosphoryl-(phosphonyl)-ha1ide of the general formula in which R has the meaning stated above, and

R is alkyl with l to 6 carbon atoms, preferably lower alkyl and especially alkyl with 1 to 4 carbon atoms,

is condensed with acetonitrile in the presence of a base and, after completion of the reaction, there is added to the reaction mixture (preferably without isolation of the intermediate product) a phosphoryl-(phosphonyl)-halide of the Formula V, optionally in the presence of a solvent;

(c) In the case in which R is alkyl and R is alkoxy, a benzoylchloroacetonitrile of the general formula H R3 No-b-b@ in which R has the meaning stated above,

is reacted with a trialkylphosphite of the general formula P(OR (VIII) (VII) in which R, is lower alkyl,

As examples of benzoylacetonitriles or their alkali metal salts and phosphoryl-(phosphonyl)-halides which may be used in the practice of the invention, there may be mentioned in particular: 2-, 3- and 4-bromo-, 2-, 3- and 4-methylmercapto-, 2,3-, 2,6-, 3,4-dichloro, 2,3,4-, 2,3,5; 2,3,6-, 2,4,5-, 2,4,6-, 3,4,5- and 3,4,6-trichloro-benzoylacetonitrile as well as (thio)-phosphoric acid 0,0-di-npropyland -n-butyl ester chloride, (thio)-phosphoric acid O-ethyl ester mono-N-ethyl-, -n-propyland -i-propylamide chloride.

The benzoylacetonitriles (IV) are partially described in the literature and the phosphoryl-(phosphonyl)-halides (V) are known. They can be prepared according to customary methods.

If the reaction is carried out in the presence of a solvent, water or practically any inert organic solvent or diluent may be used. These include preferably aliphatic and aromatic possibly chlorinated hydrocarbons, such as benzene, toluene, xylene, benzine, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene; ethers, such as diethyl ether, dibutyl ether, dioxane; ketones such as acetone, methylethyl ketone, methylisopropyl ketone and methylisobutyl ketone; and nitriles, such as acetonitri e.

If an acid acceptor is used, it may be any of the usual acid-binding agents. Particularly suitable are alkali metal carbonates and alcoholates such as sodium or potassium carbonate, methylate or ethylate; aliphatic, aromatic or heterocyclic amines, such as triethylamine or pyridine, amine, dimethylaniline, dimethylbenzylamine or pyridine. Preferably, about one molar equivalent of potassium or sodium carbonate is used relative to the reactants.

The reaction temperatures can be varied within a fairly wide range. In general, the reaction is carried out at about l0 to +100, preferably at about 20 to 60 C.

The reactions are, in general, carried out at normal pressure.

When carrying out the process, one mole of alkali metal salt of the benzoylacetonitrile concerned or one mole of the latter in the presence of about one mole of acid-binding agent is preferably used per mole of phos phoryl-(phosphonyl)-halide.

If benzoic acid ethyl ester, acetonitrile and thiophosphoric acid 0,0-diethyl ester chloride are used according to process variant (b) as starting materials, the reaction proceeds in the following sense:

(I: O a 02115 NaOCHa CHQCN (V'Ia) i Q C1-P (0 014E502 NC-CH=C ONa (IVb) (Va) As examples of usable benzoic acid esters (VI) and phosphoryl-(phosphonyl)-halides which can be used in the practice of the invention, there may be mentioned in particular: 2-, 3- and 4-bromo, 2-, 3- and 4-methylmercapto-, 2,3-, 3,4- and 2,6-dichloro-, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- 3,4,5- and 3,4,6-trichlorobenzoic acid methyl and -ethyl ester and (thio)-phosphoric acid 0,0-di-npropyland n-butyl ester chloride (thio)-phosphoric acid O-ethyl ester mono-N-ethyl, -n-propyland -iso-propylamide chloride.

The benzoic acid esters and phosphoryl-(phosphonyl)- halides to be used as starting compounds are known from the literature and can be prepared according to known processes.

The former are condensed with acetonitrile in the presence of a base, preferably an alkali metal alcoholate, to give the salts of the appropriate benzoylacetonitriles and the latter are then, preferably Without intermediate isolation, reacted with the phosphoryl-(phosphonyl)-halides, optionally in inert solvents.

As such, practically all inert organic solvents or diluents are suitable, for example, any of the classes and particular solvents mentioned above in connection with process variant (a).

The reaction temperatures may, in the case of the phosphorylation, vary within a wide range. In general, the reaction is carried out at from about 10 to 100, preferably about 20 to 60 C.

The reaction is, in general, carried out under normal pressure.

When carrying out the process, there are generally used, per mole of benzoic acid ester, 1.25 moles of aceto nitrile in the presence of 1 mole of base, preferably sodium alcoholate. After the condensation has ended, the alcohol formed during the reaction is generally distilled off. Then the mixture is, in most cases, diluted With acetonitrile or acetone, and the phosphorylation is carried out most preferably at a temperature of about 40 to 60 C.

If benzoylchloroacetonitrile and trimethylphosphite are used according to process variant (c) as starting materials, the reaction course is illustrated by the following equation:

(VIIa) (VIIIa) N CCH=C 0 CH3 (XI) As examples of benzoylchloroacetonitrile (VII) and trialkylphosphites (VIII) which can be used according to this process variant, there may be mentioned in particular: 2-meth'yl-, 2-, 3- and 4-bromo, 2-, 3- and 4-methylmercapto-, 2-chloro-4-ethylmercapt0-, 2,3-, 2,4-, 2,5-, 2,6- and 3,4-dichlorobenzoylchloroacetonitrile and trimethyl-, triethyland tri-n-propylphosphite.

The benzoylchloroacetonitriles (VII), some of which do not appear to be known, can be prepared according to known method from the appropriate benzoylacetonitriles.

When carrying out the reaction of process variant (0) it is possibe to work Without the use of solvents although inert organic solvents or diluents can be used if desired. These include preferably all aliphatic and aromatic possibly chlorinated hydrocarbons, such as benzene, xylene, benzine, chlorobenzene, toluene; and ethers, such as diethyl ether and dibutyl ether.

The reaction temperatures can be varied within a fairly wide range. In general, the reaction is carried out at from about 20 to 150, preferaby at about 50 to 100 C.

The reaction is, in general, carried out at normal pressure.

When carrying out this process variant, preferably 1 mole of benzoylchloroacetonitrile is reacted with l to 2 moles of trialkylphosphite.

The working up of the reaction mixture in the three process variants described may be effected according to customary methods.

The substances according to the invention are in most cases obtained in the form of colorless to red-colored, viscous, water-insoluble oils which can be distilled without decomposition. They can also be freed from the last volatile components by so-called slight distillation, i.e. prolonged heating at moderately elevated temperatures under reduced pressure, and in this way be purified. The refractive index as Well as the elementary analysis is particularly useful in helping to characterize the compounds.

As already mentioned, the compounds according to the invention are distinguished by an outstanding acaricidal and insecticidal effectiveness against plants pests, hygiene pests and pests of stored products, as well as ectoparasites. They possess a good activity both against sucking and biting insects and mites. They also exhibit a fungicidal and bactericidal effectiveness. Moreover, some of the compounds according to the invention may be used as rodenticides.

To the sucking insects contemplated herein there belong, in the main, aphids (Aphidae) such as the green peach aphid (Myzus persicae), the bean aphid (Doralis fabae), the bird cherry aphid (Rhopalosiphum padi), the pea aphid (Macrosiphum pisi) and the potato aphid (Macrosiphum solanijoliz'), the current gall aphid (Cryptomyzus korschelti), the rosy apple aphid (Sappaphis mali), the mealy plum aphid (Hyalopterus arunainis) and the cherry black-fly (Myzus cerasi); in addition, scales and mealybugs (Coccina), for example the oleander scale (Aspidiotus hederae) and the soft scale (Lecanium hesperidum) as well as the grape mealybug (Pseudococcus maritimus); thrips (Thysanoptera), such as Hereinalhrips femoralis, and bugs, for example the beet bug (Piesma quadrata), the red cotton bug (Dysdercus intermedius), the bed bug (Cimex lectularius), the assassin bug (Rhodnius prolixus) and Chagas bug (Triatoma infestans) and, further, cicadas, such as Euscelis bilobatus and Nephotettix bipunctazus; and the like.

In the case of the biting insects contemplated herein, above all there should be mentioned butterfly caterpillars (Lepidoptera) such as the diamond-back moth (Plutella maculipemzis), the gypsy moth (Lymantria dispZzr), the brown-tail moth (Euproctis ohrysorrhoea) and tent caterpillar (M alacosoma neustrz'a); further the cabbage moth (Mamestra brassicae) and the cutworm (Agrotis segetum), the large white butterfly (Pieris brassfcae), the small Winter moth (Cheimatobia brumata), the green oak tortrix moth (T ortrix viridana), the fall arrnyworm (Laphygma frugiperda) and tobacco cutworm (Prodenia litura), the ermine moth (Hyponomeuta padella), the Mediterranean flour moth (Ephestia kt'ihniella) and greater wax moth (Galleria mellolzella); and the like.

Also to be classed with the biting insects contemplated herein are beetles (Coleoptera), for example the granary Weevil (Sz'toplzilus granarius=CaIandra granaria), the Colorado beetle (Liptinotarsa decemlineam), the dock beetle (Gaslroplzysa viridztla), the mustard beetle (Phaedon cochlearz'ae), the blossom beetle (Meligetlzes aeneus) the raspberry beetle (Byturzts romenlosus), the bean weevil (Bruchidius=Acanrhoscelides obrectus), the leather beetle (Dermestes frz'schz'), the khapra beetle (Trogoderma granarimn), the flour beetle (Tribolz'um caslaneum), the northern corn billbug (Calandra or Sitophilus zeamais), the drugstore beetle (Stegobil-zm paniceum), the yellow mealworm (Tenebrz'a molitor) and the saw-toothed grain beetle (Owzaephilus surizzamensis), and also species living in the soil, for example wireworms (Agriotes spec.) and larvae of the cockchafer (Melolontha melolontha); cockroaches, such as the German cockroach (Glattella germalzica), American cockroach (Periplaneta antericana), Madeira cockroach (Leucophaea or Rlzyparobia maderae), oriental cockroach (Blatta orientalz's), the giant cockroach (Blaberus giganzeus) and the black giant cockroach (Blaberus fuscus) as Well as H ensc/zoutederzia flexivitta; further, Orthoptera, for example the house cricket (Aclzera domesticus); termites such as the eastern subterranean termite (Reticulitermes flavipes) and Hymenoptera such as ants, for example the garden ant (Lasius niger); and the like.

The Diptera comprise essentially the files, such as the vinegar fly (Drosophila melanogasier), the Mediterranean fruit fly (Ceratitis capitata), the house fly (Musca domestica), the little house fly Famzz'a canz'cularzs), the black blow fly (Phormz'a regina) and bluebottle fly (Calliphora erythrocephala) as well as the stable fly (Stomoxys calcitrans); further, gnats, for example mosquitoes such as the yellow fever mosquito (Aedes aegypti), the northern house mosquito (Culex pipielzs) and the malaria mosquito (Anopheles stephensi); and the like.

With the mites (Acari) contemplated herein there are classed, in particular, the spider mites (Tetranychidae) such as the two-spotted spider mite (Tetranychus telarius=Tetranychus allhaeae or Telranyclzus urticae) and the European red mite (Parazetranyc/zus pil0sus=Pan0- nyclzus ulmi), gall mites, for example the black currant gall mite (Eriophyes ribis) and tarsonemids, for example the broad mite (H emitarsolzemus latus) and the cyclamen mite (Tarsonemus pallidus); finally ticks such as the relapsing fever tick (Ornithodorus moubata); and the like.

When applied against hygiene pests and pests of stored products, particularly flies and mosquitoes, the process products are also distinguished by an outstanding residual activity on wood and clay as well as a good stability to alkali on limed substrates.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents, carriers or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as Freon; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e. g. benzene, toluene, xylene, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), paraffins (e.g. petroleum fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, etc.), amines (e.g. ethanolamine, etc.), ethers, ether-alcohols (e.g. glycol monomethyl ether, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), ketones (e.g. acetone, etc.), and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, clays, alumina, silica, chalk, i.e. calcium carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and/or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other acaricides, insecti- 'cides, fungicides, bactericides and nematocides, or rodenticides, herbicides, fertilizers, growth-regulating agents, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 0.1-95% by weight, and preferably -90% by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially' between about 0.000l%, preferably 0.0l-1% by Weight of the mixture. Thus, the present invention contemplates over-all compositions which comprise mixtures of a conventional dispersible carrier vehicle such as (1) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active elfective amount of a carrier vehicle assistant, e.g. a surfaceactive agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.0001%, and preferably 0.0l95%, by weight of the mixture.

The active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, e.g. average particle diameter of from 50- microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about 15 to 1000 g./hectare, preferably 40 to 600 g./ hectare, are sulficient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about 95% by weight of the active compound or even the 100% active substance alone, e.g. about 20-100% by weight of the active compound.

Furthermore, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. insects, acarids, ectoparasites, fungi, bacteria and rodents and more particularly methods of combating at least one of insects, and acarids which comprises applying to at least one of correspondingly (a) such insects, (b) such acarids, (0) such ectoparasites, (d) such fungi, (e) such bacteria, (f) such rodents, and (g) the corresponding habitat thereof, i.e. the locus to be protected, a correspondingly combative or toxic amount, i.e. an insecticidally, acaricidally, ectoparasiticidally, fungicidally, bactericidally or rodenticidally effective amount of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring, fumigating, and the like.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding activity of the particular new compounds of the present invention are illustrated, without limitation, by the following examples:

EXAMPLE 1 Myzus test (contact action) Solvent: 3 parts by weight acetone. Emulsifierz 1 part by weight alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Cabbage plants (Brassica oleracea) which have been heavily infested with peach aphids (Myzus persicae) are sprayed with the preparation of the active compound until dripping wet.

After the specified periods of time, the degree of destruction is determined as a percentage: 100% means that all the aphids are killed whereas 0% means that none of the aphids are killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table 1.

TABLE 1Coutinued TABLE 2-Continued Concentra- Concentlon of Degree of tration Degree of active destruction of active destruction compound in percent compound in percent Active compound 111 p.p.m. after 1 day Active compound in percent after 3 days (35) CzH O S 0.1 100 (36).- S 0.1 100 H 0. 01 95 n 0. 01 95 POC=CH (CHrCH -CHzO)zP-O-C=CH CH2 ON I CN (37)-- (CH:)2HCO S 0.1 100 \l! 0.01 90 1o POC=CH (CHa)2HCO CN EXAMPLE. 2

Phaedon larvae test Solvent: 3 parts by weight acetone. Emulsifier: 1 part by Weight alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, (10)" Q1 100 1 part by weight of the active compound is mixed with the H 100 stated amount of solvent containing the stated amount of (CZHO)ZP O? CH M01 90 emulsifier, and the concentrate is diluted with Water to the C1 0N desired concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation of the active compound until dripping wet and then infested with mustard beetle larvae (Phaedon cochlearia). G H 0 S 1 After the specified periods of time, the degree of destruc- (11) 2 igg tion is determined as a percentage: 100% means that all 0.001 60 the beetle larvae are killed. 0% means that none of the 0235 CN beetle larvae are killed. 01

The active compounds, the concentration of the active compound, the times of evaluation and the results can be seen from the following Table 2.

(16)-- 0.1 100 40 H 0.01 100 TABLE 2 (CzH O)2POC=CH 0.001 95 Phaedon larva'e test I \CN Concentration Degree of of active destruction compound in percent Active compound in percent after 3 days (0)... s ON 0.1 100 01 it I 0. 01 0 (CgHgO): OC=C tH e 0 -01 122 POC=CHON 0.001 90 (known) I 02H: (B)..- 0 0.1 100 II 0. 01 70 (CzH50)qP-0(E=Cg 1 (13)--. s 0.1 100 C] II 0. 01 100 (C2H50)2P-O-(F=QH 0.001 95 (known) ON 0.1 100 01- 0. 01 100 (C1H O)1PO(J=Cg 0.001 95 CN I (19) C2H5O S 0.1 100 i 0 C CH 0 0% CHO s 0.1 100 (6) a 5 0. 01 100 P-O-C=CH 0.001 69 C211! CN Cl- C1115 ON 15 16 TABLE 2-Continued TABLE 2C0ntinued Concen- Concentration Degree of tration Degree of of active destruction of active destruction compound in percent compound 1n percent Active compound in percent after 3 days 5 Active compound in percent after 3 days 2 s 0.1 100 32 o 0.1 100 0.01 100 0.01 100 (CzH 0)zP0(IJ=O1{ 0.001 100 (CzH O)2PO-?=OH 0N ON Cl OHaO (21)--. CzHsO\fi 0 i (33); \fi 0 6% {8g E M01 90 1 -o-o=o11\ 0.001 90 C2H5 C1 CN czHs ON CHaO C1 o H 0 1 0 (3-011 0 08i i% 1 2 a 2 M001 50 (38)... 021150 is 0 1 88 UN POC=CH 0.001 70 Br l CHaOQ (23)-- 021150 3 0.1 100 0.01 100 c/ 0-(])=CH 0.001 60 $1 0 6% :88

ON o2H50)2P-o-c=o11 (24)-- s 0.1 100 it 0. 01 100 zHrOM O- 3=CE 0.001 100 00m UN on, 40 (40)-.- s 0.1 100 II 0. 01 90 (CzH50)2PO-?=CE '8 GN i b 01 25 H0 S 0.1 100 oz 5 0.01 100 /P-0-|G=O]\E[\ 0. 001 100 02H; Cm CN S CzHs EXAMPLE 3 Tetranychus test S a: a

(CzH5O)2i -0-c=oH ,0 1 90 Solvent: 3 parts by weight acetone.

I Emulsifier: 1 part by weight alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, CH3 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount f emulsifier and the concentrate so obtained is diluted 2 H 0.1 100 8) C2 50 8 0 wlth water to the desired concentratlon.

@001 Bean plants (Phaseolus vulgaris), which have a height 0N of approximately 10-30 cm., are sprayed with the preparation of the active compound until dripping wet. These bean plants are heavily infested with spider mites (Tetranychus urticae) in all stages of development.

After the specified periods of time, the eflectiveness of S 100 the preparation of active compound is determined by (02H {L 8i 38 counting the dead mites. The degree of destruction thus obtained is expressed as a percentage: 100% means that ON all the spider mites are killed whereas 0% means that none of the spider mites are killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be (3113 seen from the following Table 3.

TABLE 3 Tetranychus test Active compound Concentration Degree of TABLE 3Contlnued Myzus test (contact action) /resistant strains Solvent: 3 parts by weight acetone. Emulsifier: 1 part by weight alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Cabbage plants (Brassica oleracea) which have been heavily infested with peach aphids (Myzus persicae) are sprayed with the preparation of the active compound until dripping wet.

After the specified periods of time, the degree of destruction is determined as a percentage: means that all the aphids are killed whereas 0% means that none of the asphids are killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table 4.

TABLE 4-Contlnued Concentration Degree of of active destruction compound in percent Active compound in perceent after 1 day PO=CH l CHBO C1 OCl 01 (known) H O S 0.1 100 (6) C2 0. 02 100 -OC=CH 0. 004. 100 l 0. 0008 65 02 5 Q CN 11 H 0 S 0.1 100 c2 5 0. 02 100 /P-O(|]=CE 00688: 122 02H; CN

(25).. CzHgO S 0.1 100 I 0. 02 100 E a: 0211. CN

(28)-- C2H50 S 0.1 100 0. 02 100 OC=CH 0.004 100 l 0. 0008 90 0211s CN EXAMPLE 5 LT test for Diptera Test animals: Aedes aegyptz'. Solvent: Acetone.

2 parts by weight of active compound are dissolved in 1000 parts by volume of solvent. The solution so obtained is diluted with further solvent to the desired lower concentrations.

2.5 ml. of the solution of active compound are pipetted into a Petri dish. 0n the bottom of the Petri dish there is a filter paper with a diameter of about 9.5 cm. The Petri dish remains uncovered until the solvent has completely evaporated. The amount of active compound per square meter of filter paper varies with the concentration of the solution of active compound used. About 25 test animals are then placed in the Petri dish and it is covered with a glass lid.

The condition of the test animals is periodically observed. The time which is necessary for a 100% destruction is determined.

The test animals, the active compounds, the concentrations of the active compounds and the periods of time at which there is a 100% destruction can be seen from the following Table 5.

TABLE 5 L ioo test for Diptera Concentration of the active compound of the solution Active compound in percent Ltioo Ofi(0Cz s)2 (known) (0)... NC CE; 0.2 3

HO=C\ o-fi-(OCEO:

(known) HC=C NJ: /0 CaH;

3 0.2 60' 0.02 120' 0.002 180' H(lJ=C' NC l fi-(OCH3)2 HC=C- CH; N I

L N i|\ S CHI HC=C N (Lfi( C2Hs)2 HC=C NC -fi(OCzHs)z HC=C TABLE -Continued Concentration oithe active compound of the solution Active compound in percent Ltioo H(iJ=C 01 -Cl NC I O-IgP|-(OC2H5):

CHaO- 0.02 120' OCzHl No Cl C] 0.02 120 HC=C N i /OC2H| T\ HC=C NJ) (L /OC1H i\ EXAMPLE 6 LDmo tCSt Test animals: Blatta orientalis. Solvent: Acetone.

2 parts by weight of the active compound are dissolved in 1000 parts by volume of the solvent. The solution so obtained is diluted with further solvent to the desired concentrations.

2.5 ml. of the solution of the active compound are pipeted into a Petri dish. On the bottom of the Petri dish there is a filter paper with a diameter of about 9.5 cm. The Petri dish remains uncovered until the solvent has completely evaporated. The amount of active compound per square meter of filter paper varies with the concentration of the solution of active compound used. test animals are then placed in the Petri dish and it is covered with a glass lid.

The condition of the test animals is observed 3 days after the commencement of the experiments. The destruction is determined as a percentage.

The active compounds, the concentrations of the active compounds. the test animals and the results can be seen from the following Table 6.

(known) TABLE 6Contlnued Concentrations of active compound percent Destrucstrength tion in Active compound solution percent O-P-(O C2 02 g T 0 C H a s N (3).... 0.2 100 0.02 100 0.002 0 H(|J=C- NC 3 HC=C N(I) (L /0C2Hs i|\ S CzHs HC=C Na 1 IllT-(0 C2 5) 2 (1) 0. 2 100 0.02 100 0. 002 0 H$=C- N. (L

1H (0 CzHu):

HC=C- O C H N5 J 2 i\ HC=C 01 Ni 1 -PO CzH S CgHs EXAMPLE 7 LD 100 test Test animals: Sitophils granarius Solvent: Acetone.

2 parts by weight of the active compound are dissolved in 1000 parts by volume of the solvent. The solution so obtained is diluted with further solvent to the desired concentrations.

2.5 ml. of the solution of the active compound are pipetted into a Petri dish. On the bottom of the Petri dish there is a filter paper with a diameter of about 9.5 cm. The Petri dish remains uncovered until the solvent has completely evaporated. The amount of active compound per square meter of filter paper varies with the concentration of the solution of active compound used. 25 test animals are then placed in the Petri dish and it is covered with a glass lid.

The condition of the test animals is observed 3 days after the commencement of the experiments. The destruction is determined as a percentage.

The active compounds, the concentrations of the active compounds, the test animals and the results can be seen from the following Table 7.

TABLE 7 Concentrations of active compound,

percent Destrucstrength tion in Active compound solution percent;

()... N C CH; 0. 2 0

I C=0\ Q O-lg-(O CzHr):

(known) HC=C N (I: l /0 02110 R g CzHn (3).-.. 0. 2 100 0.02 100 0. 002 100 0. 0002 0 H(I =C N G OP-(O CHa) a HC=C l I 002115 NC O l (41)-.. 0. 2 100 0 CH; 0. 02 100 0. 002 80 H(|l=C NC THC-=0- C 2: NC

42 0.2 100 O 0 Hg 0. 02 95 HC=C NJ} /0 02115 P TABLE 7Continued Concentrations of active compound,

percent Destrucstrength tion in Active compound solution percent H(|J=C- CH: N O

HO=O CHa -fi-(0 0211 g (28) 0. 2 0. 02 100 0. 002 0 H(I3=C- CH3 N C O-PCaH S O 02H;

HC=C

-P-O 0 H (24)... 0. 2 100 CH; 0. 02 100 0. 002 0 H(|!=C- N. J)

-{| (O OaHs);

H 0:0- NA (1).... 0 2 100 O 100 0. 002 100 0. 0002 95 H(IJ=O- N C --fi (0 C 2H a HC=C 01 TABLE 7-C0ntlnued Concentrations of active compound,

percent Destrucstrength tlon in Active compound solution percent HC])=C- N. l

(33).... O. 100 CHaO- 0. 02 100 0. 002 0 HC=C N6 (L 0 CiHl i\ S C2H| HC=C /0 0111. 'i\

S cam HC=C- NJ} I /0 CaHl 1 O CzHl NC S C2H| H(I3=C- N C EXAMPLE 8 Mosquito larvae test Test insects: Aedes aegypti (5th larval stage).

Solvent: 99 parts by weight acetone.

Emulsifier: 1 part by weight benzylhydroxydiphenyl polyglycol ether.

To produce a suitable preparation of active compound, 2 parts by weight of the active compound are dissolved in 1000 parts by volume of the solvent containing the amount of emulsifier stated above. The solution thus obtained is diluted with water to the desired lower concentrations.

The aqueous preparations of the active compounds are placed in glass vessels and about 25 mosquito larvae are then placed in each glass vessel.

After 24 hours, the degree of destruction is determined as a percentage. 100% means that all the larvae are killed. 0% means that no larvae at all are killed.

The active compounds, the concentrations of the active compounds, the test insects and the results can be seen from Table 8.

TABLE 8 Mosquito larvae test Concentration of active com- Degree 0! pound of the destrucsolution in tion in Active compound p.p.m. percent (B).-. 10 100 C1 C1 1 60 0. 1 0

HC=C

-fi-( al s):

(known) (0) N C /C H: 10

C=C\ 3 0-1-(0 CaHr):

(known) HC=C Ne} J) /0 C211;

g CIH HC=C NO L i( 0 0 z) a (41) l 100 O CH; 0. 1 40 H(\J=C NC l -fi( 2 a 1133:0- NO L fi' C 2 5) H(|3=C N C fi H5) 2 (20).-. 0. 1 CI 0. O1 90 11?:0- Cl NC I 0-1; (0 C 2H5) a HC=C NJ) (L /0 C 2H i\ TABLE 8Continued Concentration of active com- Degree of pound of the destrucsolution in tion in Active compound p.p.m. percent 11?:0- Cl NC ]l:i-0C2H5 I 002E NC II S C2 J H5 NC OCaH H(IJ=C OH: NC A fi( 2 's):

H(|3=C OH; NC 1 -1| C3Hl HC==C- NJ} (L /0 02H; i\

S CHI (24)... 0.1 100 CHs- 0.01 70 HC=C -Il(O can,

HC=C N6 i /OC2H| i\ HC=C N. (L

28 EXAMPLE 9 Test with parasitizing fiy larvae Solvent: 35 parts by weight ethyleneglycolmonomethyl ether.

Emulsifier: 33 parts by weight nonylphenolpolyglycol ether.

To produce a suitable preparation of active compound, 30 parts by weight of the active substance concerned is mixed with the stated amount of solvent which contains the above mentioned proportion of emulsifier, and the concentrate so obtained is diluted with water to the desired concentration.

About 20 fly larvae (Lucilia cuprina) are put into a test-tube which contains about 1 cc. of horse musculature. 0.5 ml. of the preparation of active compound are applied to this horseflesh. After 24 hours, the degree of destruction is determined as a percentage. means that all, 0% that no, larvae have been killed.

The active compound tested, the concentration applied and the test results obtained can be seen from Table 9.

TABLE 9 Test with parasitizing fly larvae Concentration of Degree of active destruction compound in percent Active compound in p.p.m. after 1 day NCOH=CO-l| (0 C m);

(16).-- Cl 300 100 30 100 Q 3 0 NC-CH=C--O-P (O CzHs) a NG-CH=C-O-PO 0 B;

NO-CH: 0}| (0 0113):

(41)-.. 0 OH; 300 100 30 100 Q 3 100 NC-CH: ---0%; (0 OzHm 29 TABLE 9-Cont1nued TABLE 9--'Continued Concentra- Concentration of Degree of tion of Degree of active destruction active destruction compound in percent compound in percent Active compound in p.p.rn. after 1 day Active compound in p.p.m. after 1 day NU-CH=G L- w 01H): NC-CH=C-01|0C2Hi (38).- 300 100 OCH: 3% 108 as 00H 300 100 'F NCCH=C--O1T CHa NCCH=C-OP (OC2H5); 300 100 l $3 8 29 on, 300 100 30 3g 108 I NCCH=CO-IfiOCfil Q NC-CH: -OP(OC2H:)2

(37).- 300 100 (44).. 300 100 100 100 OOH: 30 50 30 100 a o 10 100 3 0 NC-CH=C l NC-CH=C-OP(OCH(CH3)2)2 l|EI(OC2Ha)2 l 30 100 The following further examples are set forth to lllus- No-oH=c 0 trate, without limitation, the process for producing the active compounds according to the present invention. O-1[ |'(0C3 7n)2 EXAMPLE 10 NCCH=C- CH:

NCCH=C O 62H! Ofi(OC2 5)2 s OCzHi (1) (28)-- 300 100 so 100 a 100 NC CH=C CH: 188.5 g. (1 mole) of thiophosphoric acid 0,0-diethy1 65 ester chloride are added dropwise at 20 C. to 167 g. (l mole) of the sodium salt of w-cyanoacetophenone in 600 ml. of acetonitrile, the mixture is heated to 40 C. for 4 S 09211 hours and it is stirred for a further 12 hours at room tem'- 25) 100 perature. The reaction mixture is subsequently poured into CHa- 50 1 liter of ether and the ethereal solution is washed with water and 10%-strength bicarbonate solution. After drying of the organic phase over sodium sulfate, the solvent is drawn off and a yellow oil with the refractive index 11 =L5411 is obtained. The yield is 235 g. (79% of the theory).

31 EXAMPLEII NC--CH=C 0021B:

188.5 g. (1 mole) of thiophosphoric acid 0,0-diethyl ester chloride are added dropwise at C. to a mixture of 159 g. (1 mole) of w-cyano-2-methylacetophen0ne, 144 g. (1.05 moles) of anhydrous potassiumcarbonate and 1 liter of acetonitrile, and the mixture is heated to 60 C. for 5 hours. After cooling, the reaction mixture is filtered and the filtrate is taken up with 1.5 liters of ether. The ethereal solution is washed with water; after drying over sodium sulfate it is evaporated and the viscous residue is distilled. An oil with the boiling point 138 C./0.01 mm. Hg and refractive index in =L5388 is obtained. The yield is 153 g. (49% of the theory).

EXAMPLE 12 H O C 2H5 (16) 184.5 g. (1 mole) of 4-chlorobenzoic acid ethyl ester and 54 g. (1 mole) of sodium methylate are stirred together at 50 C. to give a homogeneous mass. Then 51.2 g. (1.25 moles) of acetonitrile are introduced at 80 C. under the surface of the reaction mixture, and the bath temperature is increased to 120 to 140 C. After 12 hours, the alcohol formed during the reaction is distilled off and the solid residue is then suspended in 800 ml. of acetonitrile by very vigorous stirring. 188.5 g. of thiophosphoric 0,0-diethyl ester chloride (1 mole) are then added dropwise to the mixture and it is heated to 50 C. for a further 8 hours. The reaction mixture is then poured into 2 liters of water, extracted with methylene chloride, the organic extract is washed with 10%-stre-ngth solution of sodium bicarbonate and then dreid over sodium sulfate. After the solvent has been drawn off, the viscous residue is distilled. A red oil With the boiling point 174 C./ 0.1 mm. Hg and refractive index n =1.5665 is obtained. The yield is of the theory.

In manner analogous with that described in Examples 10 to 12, the following compounds can be synthesized:

Refractive index or boiling point or 32 TABLEC0ntlnued Refractive index or boiling point or Constitution melting point NCCH=T CZHB S C2H5 NCCH=(II S OCzHu NC-CH -C- S NHCH;

(25) CH3 n =1.5455.

O-P-O 02135 S C2H B.P. 160 C./

0.05 mm. Hg. NCCH=C -PO C 11 S OC2H5 (28) CH3 n =l.5389.

l B.P. o.

01 mm. Hg. NCCH=O- -TI O 0211 S C2H (26)-.- CH nn =1.4981.

B.P. 164 C./

0.01 mm. Hg. NCCH=T O-P-O CzHs NC-CH=(|3- -CH O-P-0 C211! NCCH=C CH3 B.P. 150 to O-/ 0.01 mm. Hg.

OZHA

NC-CH=C CHa l-F-O C2115 O 0 02115 NCCH=C Cl B.P. 150 to 152 C./

l 0.01 mm. Hg. O-lfi-OCzHb NCCH=C C1 B.P. 162 to C./

l 0.04 mm. Hg. O-P-OCzHb O O C211 TAB LE-Con tinu ed The benzoylacetonitriles or their alkali metal salts to Constitution --PO C211 NC-CH 'T-Q Refractive index or be used as starting compounds can be obtained according bmhllg polllt or to the following methods: melting point M.P. as to 85 0. 5 EXAMPLE 13 1 =1.60 8. no 0N3. (IVb) 136 g. (1 mole) of benzoic acid methyl ester (or 150 5 g. =1 mole benzoic acid ethyl ester) and 54 g. (1 mole) of sodium methylate are heated to 80 C. on an oil bath and stirred together to give a gelatinous mass. 51 g. (1.25 moles) of acetonitrile are introduced under surface of the homogeneous mass, and the bath temperature is increased to 120 to 140 C. After 12 hours the mixture is cooled to 10 C. and the precipitated sodium salt is filtered ofl? with suction. After repeated digestion with ether, drying is nD24=L528Z elfected in a desiccator. The yield is 100 g. (60% of the theory). 25 EXAMPLE 14 O 'Im=1.5571. g

(live) 369 g. (2 moles) of 4-chlorobenzoic acid ethyl ester and 108 g. (2 moles) of sodium methylate are stirred together at C. to give a homogeneous mass. Then 102.5 g. (2.5 moles) of acetonitrile are at C. introduced below the surface of the reaction mixture, and the bath temperature is increased to to C. After 12 hours, the reaction mixture is poured into ice Water. It is ex- 40 tracted once with ether in order to remove neutral impurities and then acidified with concentrated hydrochloric 21:15.52. acid. The precipitate forming is taken up in ether.

After the ether has been drawn off, there remains a solid residue which is recrystallized from ethanol. Colorless 45 crystals of the melting point 129 C. are obtained. The

yield is 245 g. (68% of the theory).

In this manner, the following exemplary benzoylacetonitriles or their sodium salts are obtainable:

Yieldt, Anallopercen cos y of the M.P. g

Product (constitution) theory 0. method (IVb) 5O 1 NC-CH= NC-CHr-C-Q (IVd) 94 1 NC-CH=(IJ o1 TABLE-Continued Yield, Analopercent go sly the M.P., with Product (constitution) theory 0. method (IVI) NC-OH=(|3-ONa 88 1 (IVg) e1 1 N C -C H(|J- C Ha ONa (IVh) I 33 100 2 NC-C mo--c Ha (IVj) C H: 37 1 O N a (IVk) g 37 84-85 2 NC-C H -CQ N C--CH=(|J 0 C H:

(IVm) O C H3 88 1 ON a (IVn) .in- (I) 71 85 2 NC-CHz-C- O CHa (IVp) NCCH=|C-ONB 1O 1 (IVq) NC-CH=(|]-ON& 48 1 (IVr) C1 15 1 no-clhz ugsmm It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention.

What is claimed is:

1. 1 phenyl 2 cyanovinyl (thio) phosphoric or -phosphonic acid derivatives of the general formula:

in which X is oxygen or sulfur,

R is lower alkyl,

R is lower alkyl or alkoxy, phenyl or lower monoalkylamino, and

R is hydrogen, halogen, lower alkyl, lower alkoxy or lower alkylmercapto.

2. Compounds according to claim 1 in which R is alkyl with 1 to 3 carbon atoms, R is alkyl or alkoxy with 1 to 3 carbon atoms, or phenyl, or monoalkylamino with 1 to 3 carbon atoms, and R is hydrogen, chlorine, bromine, or alkyl, alkoxy or alkylmercapto with l to 4 carbon atoms.

3. A compound according to claim 1 wherein such compound is 0,0-diethyl-O-1-phenyl-2-cyanovinyl-thiophosphoric acid ester of the formula g OCZHIS (1) 4. A compound according to claim 1 wherein such compound is 0,0 diethyl O 1 (4' ch1or0phenyl)-2- cyanovinylthiophosphoric acid ester of the formula 5. A compound according to claim 1 wherein such compound is O,'O-diisopropyl-O-1-phenyl-2-cyanovinylthiophosphoric acid ester of the formula NC-CH=C 003E,

7. A compound according to claim 1 wherein such compound is O-ethyl-O-1-(2,4-dichl0r0phenyl)-2-cyanovinylethanethiophosphonic acid ester of the formula 8. A compound according to claim 1 wherein such compound is O ethyl O 1 (2 bromophenyl) 2- cyanovinylethanethiophosphonic acid ester of the formula 9. A compound according to claim 1 wherein such compound is 0,0 diethyl O 1 (2'-bromophenyl)-2- cyanovinyl-thiophosphoric acid ester of the formula No references cited.

LEWIS GO'ITS, Primary Examiner A. H. SUTTO, Assistant Examiner US. Cl. X.R. 

